Extractive distillation of ethylbenzene



Sept. 24, 1963 E. M. AMIR ETAL ExTRAcTIvE DISTILLATION oF ETHYLBENZENE Filed June 22. 1960 ATTOR EY V "www United States Patent Oli tice 3,155,017 Patented Sept. 24, 1963 3,105,017 EXTRACTIVE DISTELATIQN OF ETHYL- BENZENE Emanuel Amir and William R. Edwards, Baytown,

Tex., assigner-s, by mesne assignments, to Esso Research and Engineering Company, Elizabeth, NJ., a corporation of Delaware Filed June 22, 1960, Ser. No. 38,066 7 Claims. (Cl. 2132-395) The present invention is directed to a method for separating ethylbenzene from its mixtures. More particularly, the invention is concerned with separating ethylbenzene from its mixtures with Xylene. In its more specific aspects, the invention is concerned with a method for separating ethylbenzene by extractive distillation from the Xylenes.

The present invention may be briefly described as a method for separating a mixture consisting essentially of ethylbenzene and at least one member selected from the .group consisting of orthoxylene, metaxylene, and para- Xylene. In practicing the present invention, the mixture is distilled in the presence of a compound containing a single benzene ring substituted on the ring in at least two positions with a group selected from the chloro and nitro groups under conditions to separate a fraction enriched in ethylbenzene.

The substituents may be all chloro groups and may be two chloro groups or three or more chloro groups. The substituents may also be all nitro groups. It is also contemplated that the substituents may include both chloro and nitro groups. by chloro and nitro groups, other substituents such as alkyl, hydroxyl, and alkoxyl groups may be substituted in those positions. Preferably, the substituents are para to each other and, where more than two substituents are employed, the substituents are preferably in the 1, 2, 4 position where three substituent groups are on the benzene ring.

The problem of separating ethylbenzene from its'mixtures with the Xylenes is quite considerable in that ethylbenzene boils quite closely to the three Xylenes. To illustrate the closeness of the boiling points, reference may be had to Table I which follows:

Table I B.P. C. Ethylbenzene 136.19 p-Xylene 138.35 m-Xylene 1391.10 o-Xylene 144.41

Where all positions are not substituted two positions with an active group lselected from the chloro and nitro groups. While in the practice of the present invention at least two substituents may be on the benzene groups, it is possible to have more than two substituents and is further contemplated, in fact, preferred, to have three active substituent groups on the benzene ring. Furthermore, it is preferred that two of the substituents be para to each other and where three groups are employed, the substituents are preferably in the 1, 2, 4 position to get best results.

As illustrative of the compounds which are suitable in the practice of the present invention, reference is had to Table lI where the solvents useful in the present invention are listed and compared with other solvents. The relative volatilities (a) of ethylbenzene to paraxylene in the presence of several solvents are shown under the conditions:

Temperature, C. Ethylbenzene:paraxylenetsolvent, 1:1:2 mole ratio It will be seen in Table Il that one active group is not as effective as two or more. Also, where two active groups are present on the benzene ring, the substituents, which are para to each other, produce a greater alpha value than where the substituents are in the ortho or yother position. Furthermore, it will be clear that where three active groups are employed when they are substituted in the 1, 2, 4 position, a high alpha value is obtained.

Other compounds falling Within the purview of this invention include compounds of the nature of pentachlorophenyl-n-butyl ether and pentachlorophenyl-n-butyrate having observed alphas (a) at innite dilution at 110 C. of 1.29 and 1.25, respectively. Pentachlorophenyl acetate may also be employed. The pentachlorophenylalkyl ethers may also be used as well as the dialkyl tetrachloroo-phthalates. ln genera-l, in using the latter mentioned type of compounds, the longer the side chain, the lower is the melting point and in some cases, it may be desirable to use these types of compounds with a suitable intermediate boiling liquid such as nonarornatic hydrocarbons having a normal boiling point at least 20 C. above the highest boiling aromatic hydrocarbon present in the mixture being separated, particularly when compounds of short side chains are used.

Mixtures of two or more of the compounds of the present invention may be used as the eXtractive distillation solvent. While it is preferable to use a mixture of the compounds described and claimed herein, it is contemplated that there may be included in the solvent any melting point lowering agent which provides a desirable alpha.

The present invention will be further illustrated by reference to the drawing which is a ow sheet of a preferred mode of practicing the invention. Referring now to the drawing, numeral 11 designates a line through which a C8 aromatic feed, suitably a fraction obtained from a hydroformer, and containing ethylbenzene, ortho, meta, and paraxylene is introduced into the system from a source not shown. The feed stock is introduced into fractional distillation zone :12 provided with line 14 for removal of a light fraction as an overhead fraction, line 15 for removal of orthoxylene as a bottom fraction, and with line d6 for removal of the C8 aromatic fraction containing ethylbenzene and meta and paraxylene. The fraction in line 16 is suitably passed through a cooler-condenser 17 and then routed by way of line 13 and pump 1-9 to extraction distillation zone Ztl. A portion of the material in yline 18 may suitably be pumped back to fractional distillation zone 12 to serve as and provide reilux.

It is to be understood that distillation zone 12 may involve a plurality of distillation zones or towers provided with suitable internal vapor-liquid contacting means such as bell cap trays and the like and all auxiliary equipment usually associated with the modern distillation tower.

The mixture of ethylbenzene and at least one member of the group of ortho, meta, and paraxylene ows countercurrently in extractive distillation zone 20 to a solvent, of the type illustrated, introduced into zone 20 by line 21 preferably on the top plate thereof. Extractive distillation zone 20 is provided with suitable vapor-liquid contacting meansV such as bell cap trays and the like and also is provided with a heating means illustrated by steam coil 22 and overhead line 23 and a bottom line 24. Conditions are adjusted in zone 20 to extractively distill the fraction introduced byline 1S to obtain an overhead fraction enriched in ethylbenzene in line 23 which flows to condenser 23a and thence into a reflux drum 25 from which the ethylbenzene may be withdrawn by line '26 controlled by valve 27. Preferably a portion of the ethylbenzene is pumped back into the top of Zone 20 by branch line 28 controlled by valve 29 and containing reflux pump 30. The extract from zone 20 flows by way of' line 24 into extract stripper 31 provided 'with a heating means illustrated by steam coil 32 and with .line 33 for removal of an overhead fraction and line 34 for Withdrawal of the solvent. The solvent in line 34 is suitably returned thereby by way of pump 35 to line 21 with fresh solvent being introduced into line 21 from a source, not shown, by opening valve 36.

Temperature and pressure conditions in Zone 20 may be selected to give best results with the particular solvent employed. It is contemplated that operations may be conducted at atmospheric, subatmospheric, or super- Y atmospheric pressure as may be desired. The ratio of hydrocarbons to solvent has an important effect on temperature conditions which may be used. A hydrocarbon to solvent mol ratio of 3:1 to 1:10 may be desirable. A preferred ratio is about 1:1 to 1:2.

The xylenes which may be para and metaxylenes may be withdrawn from the system by opening valve 37 in line 33 kbut preferably is introduced by line 3S controlled by valve 39 into a chiller 4d through which a suitable refrigerant ilows :by means, not shown, to reduce the temperature of the fraction to a temperature in the range from 60 to 120 F. to allow separation of the paraxylene from the metaxylene. The chilled fraction is then introduced by way of line 41 into a crystallization zone 42 from which paraxylene crystals yare recovered by way of line 43 while the filtrate containing the other xylenes maybe withdrawn by way of line 44 and line 4S controlled by lvalve 46. Preferably, however, the ltrate is reintroduced into line 11 by way of line 44 containing pump 47 and controlled by valve 48 and valve 49.

In a preferred :mode of operation, the C8 aromatic feed rather than be introduced by line 11 is introduced into the system by way of line 5i) controlled -by valve 51 and then ows by way of line 38 and valve 39 into Chiller d@ and thence by line 41 into zone 42 from which the paraxylene is removed by line 43. The filtrate containing ortho, para, and metaxylene as well as ethylbenzene then ilows by line l44 into line 11 and thence into zone 12 for removal of orthoxylenes as a bottom fraction by way of line 15. The ethylbenzene and metaxylene fraction is then iowed by Way of line 16 into extractive dis- `'llation zone 20 for separation lof ethylbenzene in line 23 and recovery thereof by way of line 27. By this mode of operation, it will be clear that a method of operating is provided by way of ywhich ethylbenzene and the xylenes may be separated and recovered.

It is to |be noted that line 11 is controlled by a valve 52 which remains closed when the feed stock is introduced by line 5d and valve 51. It is to be further noted that line 53 controlled -by valve 54 is provided for bypassing Zone 12. This operation is desirable where feed is introduced by line 50. Also, by-pass -line 55 controlled by valve 56 allows zone 12 to 'be omitted from the flow system. Actually, by-pass line 53 or 55 may be used when feed is introduced by line 50 and by-pass line v53 may be used when orthoxylene is not removed in zone 12.

In order to illustrate the practice of the present invention, comparison was made in extractively -distilling a C3 hydroformate after removal of paraxylene by crystallization in a highly ecient fractionating column. In Table III, a comparison is shown at two different reflux ratios of the yields and purities of ethylbenzene obtainable with dichlorobenzene and trichlorobenzene as compared with no solvent.

Table VIII From Table III it will be clear that with a 40:11 reflux ratio using dichloro and rtrichlorobenzene, it is possible to obtain ethylbenzene purity of greater than 99% at yields of 53.5% .and 60.1%, Whereas, withk a 25:1 reflux ratio, comparable yields are obtained with slightly less purity of the ethylbenzene product. In this case, the feed stock contained 22% ethylbenzene, 10% paraxylene, and 45% metaxylene.

Further operations lwere conducted in accordance |with the present invention. Runs were made in a 50 plate column using binary mixtures charged to the still-pot. Ethylbenzene-paraxylene .and ethylbenzene-metaxylene binary mixtures were used. Dichlorobenzene was introduced on the .top plate of the column while hydrocarbon was reuxed with no overhead take-olf. A solvent concentration vof yabout 50% was maintained on the plates. Samples of overhead `and bottom were taken at hourly in-V tervals and-the analyses are shown in Table IV.

...lA-Ww Table 1V ETHYLBENZENE-PARAXYLENE BINARY Y Percent Ethylben- Temperatures, F. zene/Percent Solvent Reliux Percent Paraxylene Time Rate, Rate, Solvent mol/hr mol/hr. on Plates Pre- Top Btms. Over- Btms. heater .Vapor head ETBYLBENZENE-METAXYLENE BINARY Percent Ethylben- Temperatures, F. zenefPercent Solvent Redux Percent Metaxylene Time Rate, Rate, Solvent mol/hr. mol/hr. on Plates Pre- Top Btms. Over- Btms. heater Vapor head When the overhead composition remains unchanged Conlrasted with the foregoing results are the following from hour lto hour, it is :assumed that the column was at data obtained under the same conditions with the cornequilibrium. At 3:00 oclock it appears that equilibrium 40 mercial 1,2,4trichlorobenzene Ias solvent: had been approached. `It will be seen that fractions enriched in ethylbenzene were obtained referring to Table 1V. Using an .assumption of a 55% plate eflciency, rela- M01 percent tive volatilities of 1.095 vand 1.115 are obtained -for the ethylbenzene-paraxylene and ethylbenzene-metaxylene 100th plate 40th plate systems, respectively.

separating ethylbenzene from the three xylenes, orthoxylene, metaxylene, and paraxylene.

In a commercial operation, two distillation columns each 3 feet in diameter and 120 :feet tall and having 60 actual plates were operated in senies -as one tower. Commercial 1,2,4-trichlor-obenzene was used as .the solvent in extractive distillation of -an ethylbenzene iraction con- Some toluene and the orthoxylene were concentrated at .the top and bottom of 4the combined tower, respectively.I

The nature and vobjects of :the present invention having been completely described and illustrated, what we wish to claim as new and useful and secure by Letters Patent is:

1. A method for separating -a C8 aromatic hydrocarbon taining para, meta, :and orthoxylene. The combined towers were operated without the solvent in one instance and with the solvent in another instance. In operations without .the solvent under total reflux, solvent-free samples taken from lthe equivalent of .the 100th and the 40th plates were analyzed with Ithe following resul-ts:

mixture consisting essentially of lethylbenzene and at least one member selected from the 'group consisting of orthoxylene, rnetaxylene, land paraxylene which comprises disltilling said mixture in the presence of a com-pound containing a single benzene ring substituted on the ring in at least two positions with a chloro group under conditions to separate a fraction enriched in ethylbenzene.

2. A method in accordance with claim 1 in which said compound is dichlorobenzene.

3. A method in accordance with claim 1 in which said 4compound is triohlorobenzene.

4. A method for separating a C8 aromatic hydrocarbon mixture consisting essentially of ethylbenzene and 'at least `one member selected from the group consisting of orthoxylene, metaxy-lene, and paraxylene which comprises distilling said mixture `countercurrently in the presence of trichlorobenzene and under conditions to separate an overhead fraction enriched in ethylvbenzene, yand re- References Cited the file of this patent COVeIDg Said OVOIhEad fIaCOD. UNITED, STATES Y PATENTS 5. A method in laccordance lwith claim 4 in which the Y' Y y Y members papaxylene. Holmes Aug- 6. A method in 'accordance with y01mm 4 in which 5 2,111,968 Ferns Maf- 22, 1938 ,the memberis metaxylene 2,118,766 Moos et al. May 24, 1938 Y 7. A method in accordance with ciam 4 in which 2,799,629 Clough et 31- July 16: 1957 the member is orthoxykane. 2,957,811 Geiser Oct. 25, 1960 

1. A METHOD FOR SEPARATING A C8 AROMATIC HYDROCARBON MIXTURE CONSISTING ESSENTIALLY OF ETHYLBENZENE AND AT LEAST ONE MEMBER SELECTED FROM THE GROUP CONSISTING OF ORTHOXYLENE, METAXYLENE, AND PARAXYLENE WHICH COMPRISES DISTILLING SAID MIXTURE IN THE PRESENCE OF A COMPOUND CONTAINING A SINGLE BENZENE RING SUBSTITUTED ON THE RING IN AT LEAST TWO POSITIONS WITH A CHLORO GROUP UNDER CONDITIONS TO SEPARATE A FRACTION ENRICHED IN ETHYLBENZENE. 